4-Fluorophenol → HCID 131712663, compound

HRID 851042Notes

Reaction equation

HRID 851042 reaction equation
[CH:1]1([C:4]([N:6]2[CH2:11][CH2:10][C@@H:9]([OH:12])[C@H:8]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)[CH2:7]2)=[O:5])[CH2:3][CH2:2]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[F:38][C:39]1[CH:44]=[CH:43][C:42]([OH:45])=[CH:41][CH:40]=1.N(C(OCC)=O)=NC(OCC)=O>C1C=CC=CC=1>[OH2:5].[CH:1]1([C:4]([N:6]2[CH2:11][CH2:10][C@H:9]([O:12][C:42]3[CH:43]=[CH:44][C:39]([F:38])=[CH:40][CH:41]=3)[C@H:8]([C:13]3[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=3)[CH2:7]2)=[O:5])[CH2:2][CH2:3]1.[CH:1]1([C:4]([N:6]2[CH2:11][CH2:10][C@H:9]([O:45][C:42]3[CH:43]=[CH:44][C:39]([F:38])=[CH:40][CH:41]=3)[C@H:8]([C:13]3[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=3)[CH2:7]2)=[O:5])[CH2:3][CH2:2]1

Participants

6

Reactant 4

HCID 97324-FluorophenolHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 13039296HCID 13039296, compound

Product 1

HCID 131712663HCID 131712663, compound

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent2×

Procedure

To a stirred mixture of 1.1 g of trans-1-cyclopropylcarbonyl-3-phenyl-4-piperidinol, 1.3 g of triphenylphosphine, 0.55 g of p-fluorophenol and 23 ml of dry benzene is added dropwise at 4° C. under nitrogen a solution of 0.86 g of diethyl azodicarboxylate in 23 ml of benzene. After stirring overnight at room temperature the solid is filtered off, washed well with benzene, and the filtrate concentrated in vacuo to a gum. The gum is taken up in about 25 ml of ether and the solution kept in a stoppered flask overnight. The colorless crystals which formed are filtered, washed well with ether, and the filtrate is diluted with ether to a volume of 50 ml. The solution is washed with 10% sodium hydroxide solution (2×10 ml) and 20 ml of saturated sodium chloride solution, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo to an oil weighing 2.27 g. This material is chromatographed on 115 g of silica gel, using ether as solvent. The product is obtained as a colorless oil which partially crystallized under high vacuum. The oily material is dissolved in about 20 ml of boiling cyclohexane and filtered hot. The filtrate is allowed to cool and stand at room temperature for 3 days, cooled and filtered to give product as a colorless solid, mp 84°-87° C. (softens 82° C.).

Workup

  1. filtrationis filtered off
  2. washwashed well with benzene
  3. concentrationthe filtrate concentrated in vacuo to a gum
  4. waitthe solution kept in a stoppered flask overnight
  5. customThe colorless crystals which formed
  6. filtrationare filtered
  7. washwashed well with ether
  8. additionthe filtrate is diluted with ether to a volume of 50 ml
  9. washThe solution is washed with 10% sodium hydroxide solution (2×10 ml) and 20 ml of saturated sodium chloride solution
  10. dry with materialdried over anhydrous sodium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo to an oil
  13. customThis material is chromatographed on 115 g of silica gel
  14. customThe product is obtained as a colorless oil which
  15. custompartially crystallized under high vacuum
  16. dissolutionThe oily material is dissolved in about 20 ml of boiling cyclohexane
  17. filtrationfiltered hot
  18. temperatureto cool
  19. waitstand at room temperature for 3 days
  20. temperaturecooled
  21. filtrationfiltered
  22. customto give product as a colorless solid, mp 84°-87° C. (softens 82° C.)

Sources & evidence

ORD record
ord-eff4e1a6817d41548a5a9d17bf2d3f40
Source dataset
uspto-grants-1983_05
Patent number
US04382141

Reaction notes

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